A method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement

Abstract

The invention belongs to the technical field of hydrometallurgy, and specifically relates to a method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement. The turbulent mass transfer enhancement technology is introduced into the cobalt, nickel and magnesium extraction and separation process, and a P507+DY319 synergistic extraction system is adopted, and the excellent cobalt and nickel separation performance of the P507 extractant and the extraction performance of DY319 that extracts cobalt and nickel but not magnesium under certain pH conditions are combined. The technology forms a turbulent state through non-steady-state pulse power, separates droplets to make materials fully contact, strengthens the extraction mass transfer process, reduces reaction time, and improves extraction efficiency. The continuous extraction method is used to omit the traditional extraction method of mixing and clarifying, reduce investment costs, save usage space, and achieve continuous, precise and automatic control, and has broad prospects for industrial application.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrometallurgy, and specifically relates to a method for turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium. Background Art

[0002] With the rapid development of new energy and high-tech industries, the demand for cobalt and nickel has increased dramatically. Metallic cobalt and nickel often exist in a closely associated form in nature and have similar physical and chemical properties. Therefore, accurate and efficient separation of cobalt and nickel has become the key to ensuring resource supply and meeting market demand. At present, the separation and purification of metal elements such as cobalt and nickel in the field of hydrometallurgy mainly adopts cascade extraction tank technology. The extraction tank consists of a mixing chamber and a clarification chamber. It is a step-by-step contact extraction equipment that relies on gravity to achieve two-phase separation. The traditional cascade extraction tank is simple and flexible to operate, and the equipment is simple to manufacture. However, in actual production, there are problems such as low extraction efficiency, poor extraction effect, multiple cascade extraction processes, large footprint, pollution escape, and difficulty in realizing equipment automation and intelligence. Summary of the invention

[0003] In order to solve the problems existing in the prior art, the main purpose of the present invention is to provide a method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement.

[0004] According to one aspect of the present invention, the present invention provides the following technical solution:

[0005] A method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement comprises the following steps:

[0006] S1, preparing a saponified organic phase containing a mixed extractant;

[0007] S2, the saponified organic phase containing the mixed extractant and the Co 2+ 、Ni 2+ Mg 2+ The mixed liquid is continuously pumped into the tower turbulent reactor to achieve reverse flow, control the flow rate and temperature, mix and extract reaction in the reactor, and then collect the loaded organic phase and the raffinate separately to achieve turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium.

[0008] As a preferred embodiment of the method for turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium described in the present invention, wherein: in the step S1, the mixed extractant is DY319 extractant + P507 extractant, and the volume of DY319 extractant accounts for 10-60% of the total amount of the extractant, preferably 30%.

[0009] As a preferred embodiment of the method for turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium described in the present invention, wherein: in the step S1, the saponified organic phase includes a mixed extractant and a diluent, and the diluent is kerosene; and the volume of the mixed extractant accounts for 5-40% of the total amount of the saponified organic phase.

[0010] As a preferred embodiment of the method for turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium described in the present invention, wherein: in step S2, the Co 2+ 、Ni 2+ Mg 2+ The mixed liquid is a sulfuric acid medium system, which comes from industrial production liquid, wherein the cobalt concentration is 20~150g / L, the nickel concentration is 0.5~5g / L, and the magnesium concentration is 0.5~5g / L.

[0011] As a preferred embodiment of the method for turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium described in the present invention, wherein: in step S2, adjusting the Co 2+ 、Ni 2+ Mg 2+ The pH of the mixed liquid is 4~6.

[0012] As a preferred embodiment of the method for turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium described in the present invention, wherein: in the step S2, the flow rate of the saponified organic phase is 10~380L / h, the flow rate of the mixed liquid is 10~380L / h, and the flow ratio of the saponified organic phase to the mixed liquid is (0.1~10):1.

[0013] As a preferred embodiment of the method for turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium described in the present invention, wherein: in step S2, the temperature is 25-60°C.

[0014] As a preferred embodiment of the method for turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium described in the present invention, wherein: in the step S2, the cobalt extraction rate is more than 99.5%, the separation coefficient of cobalt and nickel is ≥3400, and the separation coefficient of cobalt and magnesium is ≥6700, and the separation coefficient is the ratio of the concentration (g / L) of the metal elements in the organic phase and the aqueous phase.

[0015] The beneficial effects of the present invention are as follows:

[0016] The invention provides a method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement. The turbulent mass transfer enhancement technology is introduced into the cobalt, nickel and magnesium extraction and separation process, and a P507+DY319 synergistic extraction system is adopted, combining the excellent cobalt and nickel separation performance of the P507 extractant and the extraction performance of DY319 that extracts cobalt and nickel but not magnesium under certain pH conditions. The technology forms a turbulent state through non-steady-state pulse power, separates droplets to allow materials to fully contact, strengthens the extraction mass transfer process, reduces reaction time, and improves extraction efficiency. The continuous extraction method is used to omit the traditional extraction method of mixing and clarifying, reduce investment costs, save space, and achieve continuous, precise and automatic control, with broad prospects for industrial application. DETAILED DESCRIPTION

[0017] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] The present invention provides a method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement, which has the following advantages:

[0019] (1) The present invention adopts a P507-DY319 synergistic extraction system, combining the excellent cobalt-nickel separation performance of P507 and the extraction performance of DY319 that extracts cobalt and nickel but not magnesium under certain pH conditions, to achieve efficient extraction and separation of cobalt, nickel and magnesium.

[0020] (2) The present invention is different from the traditional extraction tank. The turbulent high-efficiency continuous extractor has a packed tower structure. The packing of unit height can replace the single-stage extraction tank. Under the action of non-steady-state pulse power, the liquid-liquid two phases are cut into tiny and uniform droplets by the packing, which greatly enhances the mass transfer efficiency.

[0021] (3) The extraction process of the present invention is more conducive to the separation of the aqueous phase and the organic phase by means of the difference in specific gravity in the vertical tower arrangement. Therefore, it is only necessary to set a clarification section of a certain length on the upper and lower sections of the filler to achieve continuous, rapid and thorough separation of the two phases.

[0022] (4) Turbulent mass transfer enhancement technology has unique advantages over traditional equipment. This invention can accurately and quickly adjust and control the extraction process by adjusting pulse parameters, which is easy to achieve automatic control and saves water and electricity;

[0023] (5) The turbulent tower reactor has a compact structure, occupies a small area, and has a closed reaction process, which avoids the overflow of waste gas during the production process and improves the on-site working environment. No new pollution factors are added during the test, reducing environmental risks.

[0024] The device for realizing the method of turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium of the present invention is a turbulent tower reactor, including an intermediate packing layer, a heating jacket, a turbulent flow generating pump, a metering pump and a circulating heat-insulating water pump. The turbulent flow generating pump is located at the bottom of the reactor and is one of the core components of the reactor. It generates regular motion vortices inside the reactor through regular pulse power and special structural design, thereby enhancing axial and radial mixing, and achieving the effect of enhancing heat transfer and mass transfer between fluids. The intermediate packing layer is filled with fillers, and the filling method is random stacking. The periphery of the turbulent tower reactor is wrapped with a heating jacket, and the heating jacket is connected to the circulating heat-insulating water pump through a pipeline; the saponified organic phase inlet is located below the reaction tower, connecting the saponified organic phase feed pump and the saponified organic phase storage tank; the feed liquid inlet is located above the reaction tower, and a tower top phase interface camera is provided, connecting the feed liquid feed pump and the feed liquid storage tank. The feed liquid enters the reactor from the feed liquid inlet, passes through the intermediate packing layer from top to bottom, and is extracted from the raffinate outlet at the bottom of the reactor as a continuous phase medium. The saponified organic phase passes through the middle packing layer from bottom to top, undergoes continuous two-phase exchange and phase separation with the continuous phase, and is finally overflowed and extracted from the loaded organic phase outlet section.

[0025] A method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement of the present invention comprises the following steps:

[0026] S1, preparing a saponified organic phase containing a mixed extractant;

[0027] S2, the saponified organic phase containing the mixed extractant and the Co 2+ 、Ni 2+ Mg 2+ The mixed liquid is continuously pumped into the tower turbulent reactor at a certain flow rate through the saponification organic phase feed pump and the liquid feed pump to achieve reverse flow, control the flow rate and temperature, mix and extract reaction in the reactor, and then collect the loaded organic phase and the raffinate respectively to achieve turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium.

[0028] Preferably, in step S1, the mixed extractant is DY319 extractant + P507 extractant, and the volume of DY319 extractant accounts for 10-60% of the total volume of the extractant, preferably 30%.

[0029] Preferably, in step S1, the saponified organic phase comprises a mixed extractant and a diluent, the diluent is kerosene; and the volume of the mixed extractant accounts for 5-40% of the total amount of the saponified organic phase, preferably 30%.

[0030] Preferably, in step S1, P507 (2-ethylhexylphosphonic acid mono-2-ethylhexyl ester) and DY319 (molecular formula C16H32O2) are used as synergistic extractants, kerosene is used as a diluent, and they are evenly mixed in a certain ratio and then saponified to obtain a saponified organic phase.

[0031] Preferably, in step S2, Co 2+ 、Ni 2+ Mg 2+ The mixed liquid is a sulfuric acid medium system, which comes from industrial production liquid, wherein the cobalt concentration is 20~150g / L, the nickel concentration is 0.5~5g / L, and the magnesium concentration is 0.5~5g / L.

[0032] Preferably, in step S2, the Co-containing 2+ 、Ni 2+ Mg 2+ The pH of the mixed liquid is 4 to 6, preferably 5.5.

[0033] Preferably, in step S2, the saponified organic phase flow rate is 10-380 L / h, the mixed liquid flow rate is 10-380 L / h, and the flow ratio of the saponified organic phase to the mixed liquid is (0.1-10): 1. Preferably, the mixed liquid flow rate is 160 L / h, the saponified organic phase flow rate is 320 L / h, and the flow ratio of the saponified organic phase to the mixed liquid is 2:1.

[0034] Preferably, in step S2, the temperature is 25-60°C, preferably 25°C.

[0035] Preferably, in step S2, the cobalt extraction rate is above 99.5%, the separation coefficient between cobalt and nickel is ≥3400, and the separation coefficient between cobalt and magnesium is ≥6700, where the separation coefficient is the ratio of the concentration (g / L) of the metal element in the organic phase to that in the aqueous phase.

[0036] The technical solution of the present invention is further described below in conjunction with specific embodiments.

[0037] Example 1

[0038] P507-DY319 was used as a synergistic extractant (the volume of DY319 extractant accounted for 30% of the total volume of the extractant), kerosene was used as a diluent, and the mixture was evenly saponified to form a saponified organic phase, and the composition of the saponified organic phase was 9vol%DY319+21vol%P507+70vol%kerosene; the feed liquid was a sulfuric acid system with a cobalt concentration of 70.10g / L, a nickel concentration of 1.12g / L, and a magnesium concentration of 1.87g / L, and the pH of the feed liquid was adjusted to 5.5; the saponified organic phase and the feed liquid were continuously pumped into the reactor at a feed rate of 24L / h and 48L / h, respectively, and the two phases were mixed in the reactor at 25°C and an extraction reaction occurred; a continuous extraction reaction occurred under the continuous operation of a turbulent flow generating pump and a circulating insulation water pump, and Co 2+ Entering the organic phase, Ni 2+ Mg 2+The cobalt, nickel and magnesium are extracted and separated in the aqueous phase; the loaded organic phase flows out from the overflow port at the top of the reactor, and the raffinate flows out from the bottom outlet of the reactor; at equilibrium, the Co in the loaded organic phase and the raffinate phase is tested. 2+ 、Ni 2+ Mg 2+ The content of metal ions.

[0039] Example 2

[0040] P507-DY319 was used as a synergistic extractant (the volume of DY319 extractant accounted for 20% of the total volume of the extractant), kerosene was used as a diluent, and the mixture was evenly saponified to form a saponified organic phase, and the composition of the saponified organic phase was 6vol%DY319+24vol%P507+70vol%kerosene; the feed liquid was a sulfuric acid system with a cobalt concentration of 70.10g / L, a nickel concentration of 1.12g / L, and a magnesium concentration of 1.87g / L, and the pH of the feed liquid was adjusted to 5.5; the saponified organic phase and the feed liquid were continuously pumped into the reactor at feed rates of 72L / h and 144L / h, respectively, and the two phases were mixed in the reactor at 25°C and an extraction reaction occurred; a continuous extraction reaction occurred under the continuous operation of a turbulent flow generating pump and a circulating insulation water pump, and Co 2+ Entering the organic phase, Ni 2+ Mg 2+ The cobalt, nickel and magnesium were extracted and separated in the aqueous phase. The loaded organic phase flowed out from the overflow port at the top of the reactor, and the raffinate flowed out from the bottom outlet of the reactor. The Co 2+ 、Ni 2+ Mg 2+ The content of metal ions.

[0041] Example 3

[0042] P507-DY319 was used as a synergistic extractant (the volume of DY319 extractant accounted for 40% of the total volume of the extractant), kerosene was used as a diluent, and the mixture was evenly saponified to form a saponified organic phase, and the composition of the saponified organic phase was 12 vol% DY319 + 18 vol% P507 + 70 vol% kerosene; the feed liquid was a sulfuric acid system with a cobalt concentration of 70.10 g / L, a nickel concentration of 1.12 g / L, and a magnesium concentration of 1.87 g / L, and the pH of the feed liquid was adjusted to 5.5; the saponified organic phase and the feed liquid were continuously pumped into the reactor at a feed rate of 96 L / h and 192 L / h, respectively, and the two phases were mixed in the reactor at 25 °C and an extraction reaction occurred; a continuous extraction reaction occurred under the continuous operation of a turbulent flow generating pump and a circulating insulation water pump, and Co 2+ Entering the organic phase, Ni 2+ Mg 2+The cobalt, nickel and magnesium were extracted and separated in the aqueous phase. The loaded organic phase flowed out from the overflow port at the top of the reactor, and the raffinate flowed out from the bottom outlet of the reactor. The Co 2+ 、Ni 2+ Mg 2+ The content of metal ions.

[0043] Example 4

[0044] P507-DY319 was used as a synergistic extractant (the volume of DY319 extractant accounted for 40% of the total volume of the extractant), kerosene was used as a diluent, and the mixture was evenly saponified to form a saponified organic phase, and the composition of the saponified organic phase was 12 vol% DY319 + 18 vol% P507 + 70 vol% kerosene; the feed liquid was a sulfuric acid system with a cobalt concentration of 70.10 g / L, a nickel concentration of 1.12 g / L, and a magnesium concentration of 1.87 g / L, and the pH of the feed liquid was adjusted to 5.5; the saponified organic phase and the feed liquid were continuously pumped into the reactor at feed rates of 120 L / h and 240 L / h, respectively, and the two phases were mixed in the reactor at 25 °C and an extraction reaction occurred; a continuous extraction reaction occurred under the continuous operation of a turbulent flow generating pump and a circulating insulation water pump, and Co 2+ Entering the organic phase, Ni 2+ Mg 2+ The cobalt, nickel and magnesium were extracted and separated in the aqueous phase. The loaded organic phase flowed out from the overflow port at the top of the reactor, and the raffinate flowed out from the bottom outlet of the reactor. The Co 2+ 、Ni 2+ Mg 2+ The content of metal ions.

[0045] Comparative Example 1

[0046] The difference from Example 1 is that the saponified organic phase is 30 vol% P507+70 vol% industrial kerosene.

[0047] Comparative Example 2

[0048] The difference from Example 1 is that the extraction is carried out in a mixing and settling tank (not a tower turbulent flow reactor, and turbulent mass transfer enhancement is not introduced).

[0049] Comparative Example 3

[0050] The difference from Example 1 is that the volume ratio of DY319 to P507 extractants is 100:100.

[0051] Comparative Example 4

[0052] The difference from Example 1 is that the pH of the feed solution is 3.

[0053] Comparative Example 5

[0054] The difference from Example 1 is that the saponified organic phase and the feed liquid are continuously pumped into the reactor at feed flow rates of 5 L / h and 100 L / h, respectively, and the flow ratio of the saponified organic phase to the mixed feed liquid is 1:20.

[0055] The processing results of various embodiments and comparative examples are shown in Table 1.

[0056] Table 1

[0057]

[0058] It can be seen from the embodiments and comparative examples that the present invention introduces turbulent mass transfer enhancement technology into the cobalt-nickel-magnesium extraction and separation process, and adopts a P507+DY319 synergistic extraction system, combining the excellent cobalt-nickel separation performance of the P507 extractant and the extraction performance of DY319 under certain pH conditions to extract cobalt and nickel but not magnesium; the technology forms a turbulent state through non-steady-state pulse power, separates droplets to make the materials fully contact, strengthens the extraction mass transfer process, reduces the reaction time, and improves the extraction efficiency; compared with the P507-DY319 synergistic extraction system, the P507 single extraction system greatly reduces the separation of cobalt and magnesium, and the separation performance of cobalt and magnesium is poor; the cobalt extraction rate using turbulent mass transfer enhancement technology is significantly higher than that of the mixed clarification extraction tank; the DY319 extractant content is too high, which will lead to a decrease in the separation coefficient of cobalt and nickel; when the pH of the feed liquid is not within the scope of the present invention, the separation coefficient of cobalt and magnesium is reduced.

[0059] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent structural changes made by using the contents of the present invention specification under the inventive concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement, characterized in that: The steps include: S1. Prepare a saponified organic phase containing a mixed extractant, wherein the mixed extractant is DY319 extractant + P507 extractant, and the volume of DY319 extractant accounts for 10-60% of the total volume of the extractant; S2, the saponified organic phase containing the mixed extractant and the Co 2+ 、Ni 2+ Mg 2+ The mixed liquid is continuously pumped into the tower turbulent reactor to achieve reverse flow, and the Co 2+ 、Ni 2+ Mg 2+ The mixed liquid is a sulfuric acid medium system, in which the cobalt concentration is 70.10~150g / L, the nickel concentration is 0.5~5g / L, and the magnesium concentration is 0.5~5g / L; the Co content is adjusted 2+ 、Ni 2+ Mg 2+ The pH value of the mixed liquid is 5.5-6; the flow rate and temperature are controlled, mixing and extraction reaction occur in the reactor, and then the loaded organic phase and the raffinate are collected separately to achieve turbulent mass transfer enhanced continuous synergistic extraction and separation of cobalt, nickel and magnesium; the cobalt extraction rate is more than 99.5%, the separation coefficient of cobalt and nickel is ≥3400, and the separation coefficient of cobalt and magnesium is ≥6700.

2. The method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement according to claim 1, characterized in that: In the step S1, the saponified organic phase includes a mixed extractant and a diluent, the diluent is kerosene; and the volume of the mixed extractant accounts for 5-40% of the total amount of the saponified organic phase.

3. The method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement according to claim 1, characterized in that: In the step S2, the flow rate of the saponified organic phase is 10-380 L / h, the flow rate of the mixed liquid is 10-380 L / h, and the flow rate ratio of the saponified organic phase to the mixed liquid is (0.1-10):

1.

4. The method for continuous synergistic extraction and separation of cobalt, nickel and magnesium by turbulent mass transfer enhancement according to claim 1, characterized in that: In step S2, the temperature is 25-60°C.

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